Assembly having nanoporous surface layer with hydrophobic layer

ABSTRACT

A waveguide sensor system is provided. The system includes a light source and a waveguide formed from a light transmitting material. Light from the light source enters the waveguide at an input area and travels within the waveguide by total internal reflection to an analyte area and light to be analyzed travels within the waveguide from the analyte area by total internal reflection to an output area. An optical sensor is coupled to the output area and is configured to interact with the light to be analyzed. The system includes a plurality of pores located along the outer surface within the analyte area and formed in the light transmitting material of the waveguide, and the pores are configured to enhance light interaction with the analyte within the analyte area. The pores and analyte area may be protected and/or enhanced with a hydrophobic layer overlaying the pores.

RELATED APPLICATIONS

This application is a continuation of International Application No. PCT/US18/54,064 filed on Oct. 3, 2018, which claims the benefit of priority of U.S. Application Nos. 62/617,397 filed on Jan. 15, 2018 and 62/569,152 filed on Oct. 6, 2017, all of which are incorporated by reference herein in their entirety.

BACKGROUND

The disclosure relates generally to the field of sensors, and specifically to a sensor utilizing a waveguide having a porous surface within an analyte interaction region. Generally, the amount or type of a chemical or analyte can be detected by measuring a property of light, such as intensity or wavelength, that has interacted with or has been emitted from an analyte or related detection chemicals. The measured property of the light is then correlated to a property of the analyte (e.g., type of material, amount or concentration of a particular material, etc.) such that the property of the analyte may be measured.

SUMMARY

One embodiment of the disclosure relates to a waveguide optical sensing system. The system comprises a light source configured to generate light having a wavelength and a waveguide formed from a light transmitting material. The waveguide having an input area, an output area, an outer surface and analyte area located along the outer surface. The light from the light source enters the waveguide at the input area and travels within the waveguide by total internal reflection to the analyte area and light to be analyzed travels within the waveguide from the analyte area by total internal reflection to the output area. The system includes an optical sensor coupled to the output area, and the optical sensor is configured to interact with the light to be analyzed and configured to generate a signal related to a property of light to be analyzed. The system includes a plurality of pores located along the outer surface within the analyte area and formed in the light transmitting material of the waveguide. The pores have an average pore width, wherein the average pore width is less than 30% of the wavelength.

An additional embodiment of the disclosure relates to a glass sensor system including a sheet of glass material including a first major surface and a porous area located along the first major surface. The system includes a light source directing light into a first region of the sheet of glass material such that the light travels within the sheet of glass material by total internal reflection to the porous area where the light interacts with an analyte. The system includes a light sensitive device coupled to a second region of the sheet of glass material, and the light sensitive device interacts with light traveling from the porous area by total internal reflection to the second region. The light sensitive device is configured to generate a signal related to a property of the light interacting with the light sensitive device. The porous area includes a plurality of pores formed in the glass material, and the pores have an average pore width of less than 100 nm.

An additional embodiment of the disclosure relates to a sensor waveguide configured for use as part of a sensing system. The sensor waveguide includes a sheet of light transmitting material that includes a first major surface, a second major surface opposite the first major surface and an analyte contact area located on the first major surface. The sensor waveguide includes a plurality of pores formed in the light transmitting material within the analyte contact area, wherein the pores have an average pore width of less than 100 nm. The sensor waveguide includes a layer of an analyte responsive material supported by the first major surface within the analyte contact area, and at least some of the analyte responsive material is located within the plurality of pores.

Additional features and advantages will be set forth in the detailed description that follows, and, in part, will be readily apparent to those skilled in the art from the description or recognized by practicing the embodiments as described in the written description and claims hereof, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understand the nature and character of the claims.

The accompanying drawings are included to provide a further understanding and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description serve to explain principles and the operation of the various embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an exploded view of a glass waveguide sensor according to an exemplary embodiment.

FIG. 2 is a schematic side view of the glass waveguide sensor of FIG. 1 according to another exemplary embodiment.

FIG. 3 is a detailed cross-sectional view of an analyte area of a glass waveguide sensor according to an exemplary embodiment.

FIG. 4 is a micrograph image of a porous surface of a glass waveguide sensor according to an exemplary embodiment.

FIG. 5 is a top plan view of a glass waveguide sensor according to another exemplary embodiment.

FIGS. 6A and 6B are graphs showing degree of quenching in the presence of differing levels of oxygen detected using a glass waveguide sensor according to an exemplary embodiment.

FIGS. 7A, 7B, and 7C show process steps (top row) and corresponding surface microstructure in cross-section (middle row) and plan view (bottom row), according to an exemplary embodiment.

FIGS. 8A and 8B show molecular structures.

FIG. 9 is surface profiles corresponding to process steps, according to an exemplary embodiment.

FIG. 10A is a schematic diagram of a waveguide according to an exemplary embodiment.

FIG. 10B is a digital image of a system according to an exemplary embodiment.

FIG. 11 is a graphical representation of silanized dye surface.

FIG. 12 is a graphical representation of sensor output with and without water.

FIG. 13 is a top plan view of a glass waveguide sensor according to another exemplary embodiment.

DETAILED DESCRIPTION

Referring generally to the figures, various embodiments of a sensing system that utilize a waveguide as part of its optics system are shown. In general, the sensing system includes a light source (e.g., an LED) that launches light into the waveguide, the light travels within the waveguide via total internal reflection to an analyte area located on at least one surface of the waveguide. The light interacts with the analyte, for example, directly or indirectly through an analyte responsive material, generating light to be analyzed. Light to be analyzed travels via total internal reflection from the analyte area to an optical sensor (e.g., CCD, photodiode, etc.), which generates a signal related to a property (e.g., intensity, wavelength, etc.) of light to be analyzed.

In the embodiments discussed herein, the waveguide includes a plurality of pores (e.g., nanopores) located along the surface of the waveguide within the analyte area. In various embodiments discussed herein, the pores are sized (e.g., depth, width, diameter, etc.) or shaped to facilitate/improve function of the waveguide based sensor. For example, it is believed that the pores increase the surface area within the analyte area, which in turn increases the area available for the light within the waveguide to interact with the analyte or with the analyte responsive material. Further, in embodiments that utilize an analyte responsive material coated to the outer surface of the waveguide, the pores increase the surface area available for supporting the analyte reactive material as well as the portion of the analyte material exposed to interaction with the analyte (at least compared to a surface without pores). It is believed that the increased surface area and light interaction provided by the porous surface discussed herein increases the sensitivity of the waveguide sensor discussed herein.

While the pores are sized to be large enough to provide the surface area and light interaction benefits discussed above, the pores discussed herein are sized to be small enough to allow the light transmitting component to function as a waveguide. In various embodiments, the pores are sized relative to the wavelength of the light from light source such that the light is allowed to efficiently propagate within the light transmitting material via total internal reflection. In various embodiments, the light transmitting material may be glass, ceramic, plastics, etc. that allow for light conduction via total internal reflection. For example, in various embodiments, pores are sized such that the diameter and/or depth of the pores are less than the wavelength of the light from the light source and/or are less than the wavelength of the light to be analyzed. Applicant has found that by sizing pores as discussed herein to be smaller than the wavelength of the light within glass waveguide, the amount of scattering and/or outcoupling of light along the surface of the waveguide can be reduced/eliminated allowing the glass to function efficiently as waveguide. Thus, Applicant has developed a design for a porous surface waveguide that strikes a balance between providing pores that allow the glass to function efficiently as a waveguide while at that same time providing the surface area and light interaction benefits discussed above.

Further, in various embodiments, the pores of the waveguide based sensor system discussed herein are formed directly into the glass material at the surface of the waveguide, rather than including a separate porous outer layer (e.g., anodic alumina) applied onto a surface of the glass of the waveguide. Thus, the waveguide based sensor system discussed herein provides a monolithic waveguide arrangement in which light within the waveguide is permitted to interact directly with the analyte or the analyte responsive material without traversing into or interacting through a separate outer porous coating layer. In at least some embodiments, it is believed that this monolithic arrangement provides for improved light to analyte interaction which in turn improves sensor performance while at the same time providing a robust and thermally stable structure that eliminates issues that may be present with a coating layer. Further, the monolithic arrangement discussed herein eliminates the processing complexity typically associated with depositing an additional coating layer on the glass.

Referring to FIG. 1, a waveguide optical sensing system, for example a waveguide based glass sensor system 10, is shown according to an exemplary embodiment. Sensor system 10 includes a waveguide formed from a light transmitting material, shown as glass sheet 12. In other embodiments, the light transmitting material may be any suitable waveguide material, including ceramic, plastics, etc. that allow for light conduction via total internal reflection. As described in more detail below, glass sheet 12 acts as a pathway to direct and contain light traveling between the various components of sensor system 10.

Sensor system 10 includes a light source 14 that directs light, shown graphically as the arrow labeled 16, into glass sheet 12. In various embodiments, light source 14 may be a broad spectrum light source, such as a white light LED, and in other embodiments, light source 14 may be a narrow spectrum light source generating a particular spectrum of light to be used for a particular application, such as a blue light LED. As will be understood, in some embodiments, the wavelength(s) of light generated by light source 14 are selected based on suitability for detection/interaction with a desired analyte and/or for interaction with a particular analyte responsive material. In FIG. 1 light source 14 is shown spaced from glass sheet 12 to better show the components of sensor system 10, but in an exemplary embodiment, light source 14 closely abuts or contacts glass sheet 12 to increase the portion of light generated by light source 14 that is received into glass sheet 12. In some embodiments, light source 14 is bonded to (or otherwise in intimate contact with) glass sheet 12 such that light from light source 14 is coupled into the glass sheet, and in such embodiments, a light coupling structure (e.g., a prism coupler, a scattering material, etc.) is not utilized to couple light into the glass. However, in some other embodiments, glass sheet 12 may include one or more light coupling structure (e.g., a prism coupler, a scattering material, etc.) which facilitates coupling of light from light source 14 into glass sheet 12.

In the embodiment shown, sensor system 10 includes an analyte area 18 that can support or otherwise come into contact with a material to be analyzed, shown as analyte 20. In general, light 16 travels within glass sheet 12 via total internal reflection from light source 14 to analyte area 18 where light 16 interacts with analyte 20 (either directly or indirectly) resulting in the yield, production, generation or alternation of light to be analyzed, shown graphically by the arrow labeled 22. In at least some embodiments, by utilizing glass sheet 12 as a waveguide, the interaction between the light with the system and the analyte is increased by the multiple reflections that occur as the light travels within the waveguide. As shown in the embodiment of FIG. 1, analyte area 18 occupies a portion, less than the entire area of the upper surface of glass sheet 12.

In general, light to be analyzed 22 travels via total internal reflection within glass sheet 12 to an optical detector or sensor, shown as photodiode 24. As will be understood, photodiode 24 is a device which interacts with light to be analyzed 22 and generates a signal 26 (e.g., an electronic signal) related to a property of light to be analyzed 22 (e.g., intensity, wavelength, etc.). It should be understood that in various embodiments, the light sensitive device of sensor system 10 may include any suitable light sensitive device, including charge coupled devices (CCDs), photodiodes, photodiode arrays, photoconductors, phototransistors, photomultiplier tubes, etc.

Signals 26 are received and processed by a processing circuit, such as processor 30. In general, processor 30 is configured with hardware and/or software for receiving signals 26 and for processing signals 26 to determine one or more characteristic (e.g., presences, amount, concentration, type, etc.) of analyte 20. In various embodiments, processor 30 can include a wide range of hardware and/or software that receives and processes signals 26. For example, in some embodiments, data acquisition and processing includes DC measurement of the resulting photocurrent from photodiode 24 when light source 14 is turned on. In other embodiments, data acquisition and processing includes various modulated approaches that are capable of phase shift measurements or low signal measurements with interference (e.g. ambient light) rejection. In various embodiments, processor 30 may be a processor of a portable general purpose computing device, such as a smartphone, tablet, smartwatch, smartglasses, laptop, etc. In other embodiments, processor 30 may be the dedicated processor (e.g., a dedicated processor, microprocessor, ASIC, etc.) of a dedicated sensor system.

In general, sensor system 10 may be a wide variety of sensing systems configured to measure, detect or monitor a wide variety of analytes. For example, sensor system 10 may be configured to measure, detect or monitor various gases, chemicals, liquids, biomarkers, etc. In addition, in some embodiments, sensor system 10 may include multiple analyte areas 18 each configured to detect or measure a different analyte and/or different properties of the same analyte. In some such embodiments, each of the different analyte areas 18 may include different analyte responsive materials for interacting with the desired analyte. In other embodiments, system 10 may be configured for other light analysis applications, such as spectrophotometer applications.

Referring to FIG. 2, a side view of a sensor system 10 is shown according to an exemplary embodiment. Glass sheet 12 includes a first major surface, shown as upper surface 32, and a second major surface, shown as lower surface 34. As shown schematically in FIG. 2, light 16 and light 22 travels via total internal reflection within the thickness of glass sheet 12. In this arrangement, analyte area 18 is located on or is formed in upper surface 32, and both light source 14 and photodiode 24 are located along or are supported from lower surface 34. In the embodiment shown, light source 14 is in contact with lower surface 34 such that light 16 is allowed to efficiently enter glass sheet 12, and photodiode 24 is located along lower surface 34 such that light is able to exit glass sheet 12 to interact with photodiode 24. Further, in this arrangement, analyte area 18 is located between light source 14 and photodiode 24, and specifically light source 14 and photodiode 24 are located along opposite edges of glass sheet 12.

As noted above, glass sheet 12 acts as an optical waveguide such that light is carried between the different components of sensor system 10 via total internal reflection. Accordingly, in this arrangement glass sheet 12 has an input area 36 at which light source 14 is located and an output area 38 at which photodiode 24 is located. Thus, in this arrangement, glass sheet 12 acts as a waveguide carrying light 16 within glass sheet 12 from input area 36 to analyte area 18. At analyte area 18, light 16 within glass sheet 12 interacts, either directly or indirectly, with analyte 20 on upper surface 32 (e.g., via evanescent light interaction, via optical coupling due to index matching, critical angle change when analyte 20 is a liquid, absorption, photoluminescence, etc.) yielding light to be analyzed 22. Glass sheet 12 also acts as a waveguide directing light to be analyzed 22 toward output area 38 where the light 22 interacts with photodiode 24.

In some embodiments, glass sheet 12 as a whole acts as the waveguide. In some other embodiments, glass sheet 12 as a whole may not act as the waveguide but may include waveguide sections or embedded waveguides. For example, the glass waveguides discussed herein may be laser written waveguide sections within glass sheet 12 and/or ion-exchange waveguides embedded within glass sheet 12.

Further, in some embodiments as shown in FIG. 2, the analyte area 18 occupies the entire area of surface 32, and in other embodiments, analyte area 18 occupies less than all of the area of surface 32. Glass sheet 12 includes a thickness, T1, between upper surface 32 and lower surface 34. In particular embodiments, T1 is between 20 micrometers and 4 millimeters, and specifically is between 20 micrometers and 2 millimeters. In the embodiments shown, surface 32 (except for the pores discussed herein) and surface 34 are substantially planar, parallel surfaces, and in other embodiments, surface 32 and/or surface 34 may be a convex or concave curved surfaces, may be angled relative to each other or may include other complex curves or shapes.

Referring to FIG. 3, a schematic cross-sectional view of analyte area 18 is shown. Glass sheet 12 includes a plurality of pores 40 formed in the glass material of sheet 12 and located along outer surfaces 32 within analyte area 18. As shown in FIG. 3, pores 40 may be wells, recesses, channels, depressions, etc. formed along outer surface 32 of glass sheet 12. In general, pores 40 are sized and/or positioned along surface 32 in a manner that increases or improves the ability of light traveling within glass sheet 12 to interact with an analyte while at the same time allowing glass sheet 12 to function as a waveguide. It should also be understood, that while the schematic view of FIG. 3 shows pores 40 as a substantially consistent well-like structure for ease of depiction, pores 40 may be an interconnected sponge-like three dimensional, network of pores located adjacent one or more surface of glass sheet 12, as shown in FIG. 4. In particular, pores 40 are believed to increase the area of surface 32 (as compared to a nonporous, planar surface) which provides the interaction interface between the light within glass sheet 12 and the analyte, and it is believed that by increasing the area of this interaction interface, sensor system 10 provides a more sensitive and/or more accurate ability to sense an analyte within analyte area 18. Further, in contrast to some materials that utilize a porous coating applied to a glass or ceramic material (e.g., a porous anodic alumina coating), pores 40 provide the increased light/analyte interaction area in a monolithic structure without the need for a separate additional layer. Applicant also believes that the monolithic construction and pore arrangement discussed herein provides for a thermally stable sensor system, lends itself to thin device applications and/or lends itself for use with multiplexed detecting materials.

In various embodiments, pores 40 are specifically sized large enough to provide this increased light/analyte interaction area, while at the same time sized relative to the wavelength of light 16 from light source 14 and/or to the wavelength of light to be analyzed 22 to limit or prevent scattering or outcoupling that may otherwise occur along a porous waveguide surface. In various embodiments, pores 40 have an average pore width, shown representatively as W1, and an average pore depth, shown representatively as D1. In general, average pore width W1 is average of the dimension perpendicular to the thickness of glass sheet 12 for the pores 40 of analyte area 18, and in embodiments where pores 40 are substantially circular in cross-section, W1 represents an average diameter. In general, average pore depth D1 is the average of the pore dimension parallel to the thickness of glass sheet 12 for the pores 40 of analyte area 18.

In various embodiments, W1 is less than 30% of the wavelength of light 16 and/or of the wavelength of light 22, specifically less than 10% of the wavelength of light 16 and/or of the wavelength of light 22, and more specifically is between 1% and 9% of the wavelength of light 16 and/or of the wavelength of light 22. In some such embodiments, W1 may also be greater than 0.1% and more specifically greater than 1% of the wavelength of light 16 and/or of the wavelength of light 22. In specific embodiments, W1 is greater than 4% and less than 6% of the wavelength of light 16 and/or of the wavelength of light 22, and specifically, W1 is about 5% (e.g., 5% plus or minus 10%) of the wavelength of light 16 and/or of the wavelength of light 22. In various embodiments, W1 is less than 100 nm, and more specifically is greater than 1 nm and less than 30 nm.

In various embodiments, D1 is less than the wavelength of light 16 and/or is less than the wavelength of the wavelength of light 22, specifically less than 50% of the wavelength of light 16 and/or of the wavelength of light 22, and more specifically less than 30% of the wavelength of light 16 and/or of the wavelength of light 22. In some such embodiments, D1 may also be greater than 5% and more specifically 10% of the wavelength of light 16 and/or of the wavelength of light 22. In various embodiments, D1 is between 10 nm and 10 μm.

In various embodiments, pores 40 increase the surface area of surface 32 as compared to a planar nonporous surface. In various embodiments, the area of surface 32 is 200% greater, 300% greater, or 500% greater than a nonporous planar glass surface having the same outer dimensions as analyte area 18. In specific embodiments, the area of surface 32 is between 400% and 1000% greater than a nonporous planar glass surface having the same outer dimensions as analyte area 18. In a particular embodiment, the percentage of free space or air within the porous zone of glass sheet 12 can be more than 30%, more than 50% and more than 75%, and in such embodiments the degree of porosity can be defined in terms of the percentage of free space in the network.

In some embodiments, sensor system 10 may be configured to allow light 16 to interact directly with an analyte at surface 32, and in some such embodiments, light within glass sheet 12 interacts with the analyte via evanescent light interaction, via optical coupling due to index matching, via critical angle change or via absorption.

In other embodiments, sensor system 10 includes a layer of analyte responsive material supported by surface 32 and located at least in part within pores 40. In general, analyte responsive material is any material that interacts with light 16 and/or analyte 20 such that light to be analyzed 22 is related to or varies based on a property of analyte 20 (e.g., presences/absence, amount, concentration, etc. of analyte 20). In such embodiments, by coating pores 40 with the analyte responsive material the portion of the analyte responsive material available to interact with light 16 at the interface between the glass and the analyte responsive material is increased. Similarly, by coating pores 40 with the analyte responsive material the portion of the analyte responsive material available to interact with analyte 20 at the interface between the analyte and the analyte responsive material is increased.

As shown in FIG. 3, the analyte responsive material may be a fluorescent analyte responsive material, shown as a layer of analyte sensitive fluorophore material 42. In this embodiment, analyte sensitive fluorophore material 42 is applied in a layer, coating surface 32 and located within pores 40 within analyte area 18. In a particular embodiment, analyte sensitive fluorophore material 42 is a material that is excited by light 16 causing fluorescence and in which an intensity or other characteristic of the fluorescence generated by analyte sensitive fluorophore material 42 varies in the presence of the analyte. In this manner, light to be analyzed 22 includes the fluorescent light from analyte sensitive fluorophore material 42 and the intensity or other property of the fluorescent light is related to the presence or amount of the analyte located at analyte area 18.

In a particular embodiment, analyte sensitive fluorophore material 42 is an O₂ sensitive fluorophore, and in a specific embodiment, analyte sensitive fluorophore material 42 is an Ru-complex, such as tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) dichloride. In such embodiments utilizing this analyte reactive material, analyte 20 is oxygen, and fluorescence of the analyte sensitive fluorophore material 42 is reduced (e.g., via quenching) in the presence of oxygen and the degree of fluorescence reduction is related to the amount of oxygen present at analyte area 18. Thus, in such embodiments, the intensity of the fluorescent component of light to be analyzed 22 is related to the amount of oxygen present to interact with analyte sensitive fluorophore material 42. In this arrangement, the signal 26 generated by photodiode 24 is related to the amount of atmospheric oxygen present at analyte area 18, which can be read and processed by processor 30.

It should be understood, that while FIGS. 1-3, show a sensor system in which analyte area 18 is an outer or upper surface of glass sheet 12, other glass waveguide sensor arrangements are contemplated utilizing the nanoporous surface arrangements discussed herein. For example, in one embodiment, sensor system 10 includes a porous analyte area 18 in the center of a glass waveguide arrangement formed by pressing two glass sheets coated with an analyte responsive material together with sufficient flatness to maintain waveguided modes in both glass layers. In other embodiments, glass sheet 12 may be a multilayer (e.g., a two or three layer) fusion formed glass sheet, and in a specific embodiment, one or more of the glass layers of the multilayer glass sheet is a layer of leached Vycor glass available from Corning, Inc.

In addition to pores 40, the surface within analyte area 18 may be further modified to enhance interaction of light with analyte 20. In an exemplary embodiment, sensor system 10 includes silver nanoparticles embedded in surface 32 within analyte area 18 which is believed to enhance interaction between light 16 and analyte 20 via surface enhanced Raman scattering (SERS). In such embodiments, the silver nanoparticles may be embedded in the glass in situ or may be deposited onto surface 32 after formation of pores 40.

Referring to FIG. 4, a micrograph image of pores 40 within a glass sheet 12 is shown according to an exemplary embodiment. As shown in the image of FIG. 4 and as noted above, pores 40 form a three-dimensional network of pores adjacent one of the surfaces of glass sheet 12. In the embodiment shown in FIG. 4, pores 40 are formed via a chemical etching processes. However, in other embodiments, pores 40 may be formed through any suitable process including, laser etching, photolithography, e-beam lithography, self-assembly of an etch mask, nanoimprint lithography, phase separation (e.g., detirification of Vycor glass) combined with selective etching, use of block copolymer masks, etc. In such embodiments, glass sheet 12 may be fabricated via a technique which results in glass with porous surfaces and in such embodiments, pores 40 are not formed via a secondary formation step.

Referring to FIG. 5, a waveguide optical sensing system, such as waveguide based glass sensor system 50, is shown according to an exemplary embodiment. Sensor system 50 is substantially the same as sensor system 10 except as discussed herein. Similar to sensor system 10, sensor system 50 includes an analyte area 18 that receives light 16, and light to be analyzed 22 leaves analyte area 18 to interact with photodiode 24. However, in the arrangement shown in FIG. 5, light source 14 and photodiode 24 are generally located on the same side of analyte area 18, and in particular are located adjacent to a common edge of glass sheet 12. In this arrangement, system 50 includes a light blocking structure 52 located between light source 14 and photodiode 24 such that light 16 is blocked from traveling directly from light source 14 to photodiode 24. This arrangement limits or prevents photodiode 24 from being saturated by direct light 16 allowing photodiode 24 to be responsive to or increase responsiveness to light to be analyzed 22.

Further, sensor system 50 also includes a second optical sensor, shown as second photodiode 54. In general, photodiode 54 is configured to receive light 16 from light source 14 and to generate a signal related to a property of light 16, and this signal is communicated to processor 30. Thus, in this arrangement, photodiode 54 monitors the output of light source 14 and allows operation of system 50 to be adjusted or controlled in real time in relation to the measured light output from light source 14. For example, a measured level of fluorescence from a fluorescent analyte responsive material may be related to both a characteristic (e.g., intensity, wavelength, etc.) of light 16 and to the amount of analyte present. Thus, by monitor operation of light source 14 via photodiode 54, system 50 can more accurately measure the desired property of the analyte by adjusting readings based on fluctuations in the output of light source 14.

Sensor system 50 also includes a second light blocking structure 56 located between analyte area 18 and second photodiode 54 such that light to be analyzed 22 traveling away from analyte area 18 is blocked from directly traveling to second photodiode 54. This arrangement limits or prevents photodiode 54 from experiencing cross-talk with the light to be analyzed 22, which allows photodiode 54 to be responsive to or increases responsiveness to light 16. In general, light blocking structures 52 and 56 may be any suitable structure for limiting or preventing light from reaching photodiodes 24 and 54, respectively. In various embodiments, light blocking structures 52 and 56 may be opaque physical structures, reflective structures, light absorbing structures, optical filters, etc.

In various embodiments, glass sheet 12 may be formed from a wide variety of suitable glass materials capable of functioning as a waveguide. In various embodiments, glass sheet 12 may be formed from a fusion drawn glass material, and in specific embodiments, glass sheet 12 may be EagleXG glass, Gorilla Glass, high purity fused silica (HPFS), Vycor glass or Iris Glass available from Corning, Inc. In various embodiments, glass sheet 12 may be formed in a wide range of sizes as desired for certain applications. In various embodiments, the width and/or length of glass sheet 12 may be between 5 millimeters and 250 centimeters. In some embodiments, a subsection of glass sheet 12 may be utilized as the waveguide for sensor system 10, and in other embodiments, the entirety of glass sheet 12 may be used as the waveguide for sensor system 10. In various embodiments, glass sheet 12 may configured to provide sensing in a number of different application. For example, glass sheet 12 may substrate in a dedicated sensor device, cover glass equipped with a sensor for mobile electric device, cover glass equipped with a sensor for display device, automotive glass, building/architectural glass, etc.

FIGS. 6A and 6B show data generated from operating systems such as discussed herein demonstrating that a repeatable signal proportional to O₂ concentration can be generated utilizing a glass sheet waveguide including a nanoporous analyte area supporting an Ru-complex, specifically tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) dichloride, as an analyte sensitive fluorophore material, as discussed above. In one embodiment, CH00 is the output from photodiode 24, and CH07 is the output from photodiode 54 as shown in FIG. 5. The hardware used to acquire the data in FIGS. 6A and 6B included a waveform generator, an LED/laser driver, and a lock-in amplifier. Oxygen content was varied using mass flow controllers. The data in FIGS. 6A and 6B shows clear quenching of the Ru-complex fluorescence with increasing oxygen.

According to an exemplary embodiment, a nanoporous glass fabrication method uses more than one chemical functionalization on the same glass surface that contains a thin layer of nanoporosity. The two functionalizations are (1) attaching a sensing dye coating as discussed above, and (e.g., followed by) (2) attaching hydrophobic groups on the surface of the nanoporous glass. Hydrophobicity means the property of a molecule or material to be repelled from a mass of water. As a result, functionalized (nanoporous layer containing) glass has gas sensing behavior and water repellent characteristics. Dual behaviors can be observed using the same sensing components, which may improve performance over smooth glass.

According to an exemplary embodiment, a multifunctional layer (e.g., of a sensor as disclosed above or other assemblies, such as semiconductor substrate, printed circuit board, antenna assembly) includes a nanoporous glass surface, such as a glass surface that facilitates gas sensing and where the dye is protected from moisture using hydrophobic chemical. Such an assembly in a sensor may include water sensing on the coated surface using the same optical components. Accordingly, such as combined structure may provide a type of sensing dye protection as well as an ability to determine water/moisture on the same surface.

According to an exemplary embodiment a process used to create such a surface involves two steps. One step (e.g., a first step) includes fusing a sensing medium (e.g. dye or other chemicals; for example, to sense oxygen—Ruthenium and platinum porphyrin dyes may be used, to sense formaldehyde—Fluoral P and other fluorescent sensing dye may be used). Similarly, fluorescent dye-based sensing chemical can be easily infused into a nanoporous layer (e.g., glass nanoporous structure) as disclosed herein. Another step (e.g., second step) includes creating a hydrophobic protecting layer on top of the nanoporous layer. In this approach, the nanoporous layer works efficiently, such as when compared to a smooth glass surface, to retain the sensing medium (e.g., dye) on the surface at the end of the step of creating the hydrophobic protecting layer. Also, waveguide properties of the nanoporous layer, upon multi-functionalization, remained intact and so an optical waveguide may be used to detect an analyte. According to an exemplary embodiment, a functionalized surface, using the optical elements as disclosed herein, detected gas via the sensing medium and detected the surface changes, such as addition and removal of water on the surface via hydrophobic layer. Further, the hydrophobic layer protects the dye from degrading under humid conditions by preventing dissolution of dye from the surface in water.

Referring to FIG. 7, FIG. 7(a) includes glass with nanoporous surface layer. The layer is on the order of 100 nm thick, such as at least 20 nm, such as at least 50 nm, and/or no more than 500 nm, such as no more than 300 nm. Porosity of the nanoporous surface layer is on the order of sub-10 nm porosity, such as sub-50 nm porosity, such as sub-30 nm porosity. FIG. 7(b) includes the nanoporous layer shown in FIG. 7(a), but after the surface has been modified with sensing dye, such as in a step of the manufacturing process described above. FIG. 7(c) includes the nanoporous layer after modification of the sensing dye, as shown in FIG. 7(b) and hydrophobic coating layer. According to an exemplary embodiment, the hydrophobic layer extends over a top surface, or outer surface of the nanoporous layer. According to an example embodiment, the hydrophobic layer is mostly located in a top of the nanoporous layer, extending less than half the thickness of the nanoporous layer, such as extending less than a quarter of the thickness of the nanoporous layer, such as at least some of the sensing dye in the nanoporous layer is not covered by the hydrophobic layer, such as most of the sensing dye in the nanoporous layer is not covered by the hydrophobic layer.

According to an exemplary embodiment, the sensing dye may be Ruthenium-based inorganic complex (Ru dye) for oxygen sensing, for example including molecules as shown in FIG. 8(a). According to an exemplary embodiment, the hydrophobic coating is a trichloro perfluoro octyl dimethyl silane (FOTS) to make the glass surface hydrophobic, as shown in FIG. 8(b).

Referring to FIG. 9, atomic force microscopy images of the nanoporous (NP) glass after different steps, as disclosed above, are shown to monitor the change in topography and the roughness of the surface. The following Table summarizes the measured attributes:

Roughness value from AFM Contact Glass with modification (nm) (average of 10 spots) angle NP 3.02 50.35 NP + dye 3.04 52.54 NP + dye + hydrophobic coating 2.79 110 NP + hydrophobic coating 2.71 122 G + hydrophobic coating 108 G 0.32 66 In the Table above, G stands for smooth (not nanoporous) glass, NP stands for nanoporous glass as described herein. According to an exemplary embodiment, the nanoporous glass has a roughness value of greater than 3 nm measured over an average of 10 spots, and a contact angle of greater than 50 degrees and less than that of smooth glass (e.g., 66 degrees). According to an exemplary embodiment, the nanoporous glass plus sensing dye (e.g. Ru dye) has a roughness value of greater than 3 nm measured over an average of 10 spots, and a contact angle of greater than 50 degrees and greater than that of nanoporous glass without the sensing dye, and less than that of smooth glass (e.g., 66 degrees). According to an exemplary embodiment, the nanoporous glass plus sensing dye (e.g. Ru dye) plus hydrophobic coating (e.g., FOTS) has a roughness value of less than 3 nm and/or at least 2.5 nm, such as at least 2.6 nm measured over an average of 10 spots, and a contact angle of greater than 100 degrees.

Referring to FIG. 10(a), a schematic diagram is shown to illustrate optical waveguide principle disclosed herein. For example, a phase angle based fluorescence sensing principle may be used to study multifunctional nanoporous sensing glass, as disclosed herein, for oxygen. Such a test may involve using fluorescent phenomenon and optical waveguiding in the glass.

Referring to FIG. 10(b), a digital image of such a the multifunctional surface is shown, where a light emitting diode (e.g., 450 nm) is used as an excitation source and emission from dye was collected on the photo diode. Bright spots shown in FIG. 10(b) indicate the location of dye molecule. Red filter was used on top to mask blue light from the LED when taking the image of FIG. 10(b).

Referring to FIG. 11, intensity and phase angle are an output from a photodiode, as shown in FIG. 10(a). Switching of emission (turning on/off) from the sensing dye in the multifunctional nanoporous glass is sent as a signal to the photo diode. Upon changing the environment in the testing chamber, the emission intensity changed, as shown in FIG. 11. Similarly, referring to FIG. 12, sensing in presence of water droplet on the multifunctional nanoporous glass surface, intensity shows similar response before and after water droplet addition, demonstrating that the surface is robust, where the dye has been protected.

Referring to FIG. 13, steps in creating a multifunctional nanoporous layer, may include (1) coating with a first chemical (e.g. Ru dye or other sensing dye or chemical) that is not soluble or not particularly soluble in a second solvent, and (2) coating with a second chemical with the second solvent. Applicants found that the same procedure, when applied on a smooth glass surface, resulted in removal of the dye after the second step. Accordingly, use of the nanoporous layer was able to delay and/or prevent removal of the dye with the second solvent.

According to an exemplary embodiment, a multifunctional surface was created and characterized using atomic-force microscopy, as shown in the Figures discussed above, and contact-angle measurement to confirm the coating after each step. Then, the multifunctional nanoporous glass (NP) was tested in a gas chamber for oxygen sensing. The oxygen sensing characteristics showed sensing responsivity in the presence and absence of water on the sensing surface. In addition to sensing oxygen, it also showed when water is added and evaporated from the surface. Simultaneous detection of gas and liquid present on the surface was possible because of the multifunctional nanoporous glass surface. In other embodiments, sensors disclosed herein may test for other gases or chemicals.

As mentioned above, a process for making an assembly as disclosed herein includes two steps in some embodiments. FIG. 7 shows the flow chart for such a process and also the how the nanoporous surface may be expected to change at the end of each step. FIG. 7(a) shows an image (e.g. from scanning electron microscopy) of the nanoporous layer in two perspectives: cross view and plan view. As shown in the cross-sectional view, the nanoporous layer extend about 50 to 100 nm from the top of the surface. The nanoporous glass used here was made for anti-reflective and photovoltaic application using selective etching processes.

According to an exemplary embodiment, in one step, a dye (e.g., Ruthenium or Ru dye), as shown in FIG. 8, is for optical sensing of oxygen. The Ru dye is ionic in nature and is soluble in water and polar high dielectric solvent such as methanol, ethanol and insoluble in an apolar low dielectric solvent such as hexane. The dielectric constant for the solvents are about 80.1 for water, 24.5 for ethanol, 32.5 for methanol, and 1.88 for hexane.

According to an exemplary embodiment, the nanoporous layer was impregnated using an ethanol solution of Ru dye using drop casting. A known volume (1-5 ul) Ru dye of known concentration (0.1-0.5 mM) dissolved in ethanol was drop casted on the nanoporous glass surface (NP). The glass sample size was 2 inches by 2 inches. The solvent was allowed to evaporate, thus, the Ru dye adsorbed gets on the surface. Glass surfaces tend to have negative surface charge and, and as such sensitization is an ion pairing process between a positively charged dye (FIG. 8(a)) and a negatively charged nanoporous surface. Applicants have found nanoporosity helps to increase the sensitization process efficiently by spreading the dye molecule across a higher surface area. Ethanol was selected as a solvent for this step because of its solubility and volatility.

According to an exemplary embodiment, the method for making the hydrophobic layer uses silane-based chemicals. Perfluoro octyl dimethyl dichloro silane (FOTS) (shown in FIG. 8(b)) was used as a hydrophobic layer forming chemical in this example. FOTS was mixed with hexane at a concentration of 0.5% by volume. Other known hydrophobic chemicals are contemplated. The Ru dye coated surface was dipped in the FOTS hexane solution for 30 minutes at room temperature. After 30 minutes, the glass was taken out and rinsed with clean solvent (hexane and Isopropyl alcohol) to remove unbound FOTS from the surface and heated in an oven for 15 minutes at 100° C., where the formed layer was then wiped using perfluoro (butyl-tetrahydrofuran) to clear the surface.

Notably, in this two-step process, the Ru dye used for the sensitization did not dissolve at the end of the second step, possibly due to the mismatch in the dielectric properties. Applicants believe that the nanoporous surface may facilitate this, as the nanoporous surface helps to hold the Ru dye inside the pocket/pores after the second step prevents solvent contact with the dye. For example, Applicants found that the same two-step procedure repeated on the smooth glass surface did remove the Ru dye from the surface. The chemicals used in these two steps can be expanded or altered to other chemicals for surface modification.

Referring to FIG. 9, AFM images of the nanoporous glass surface and the glass surface ends of each step are shown. AFM plan view shows the pores in the nanoporous layer are in the nanometer scale ranging from about 6 nm (or less in some embodiments) up to about 10 nm or more in some embodiments. The roughness of the nanoporous layer from the AFM topographic analysis is in the range of 3.2 nm as shown in the Table. The roughness of the nanoporous layer was 10 times higher in magnitude compared to the smooth surface. After step 1, the incorporation of Ru dye in the nanopores, the contact angle on the surface increased by 2 degrees and roughness did not change, evidencing that the dye molecules did not aggregate on the surface and the Ru dye went through the pores of the nanoporous glass. A slight increase in contact angle confirms the surface was treated with Ru dye. After the step of adding the hydrophobic coating, the roughness of the nanoporous layer decreased, which means the pores were getting filled. There was only a decrease of 7% on the roughness upon completing this step for the nanoporous layer, evidencing that the pores are not blocked in the two-step process. The real confirmation for the step-2 functionalization comes from the contact angle measurement, such as where there was a 51% increase in the contact angle: from 52 degrees to 110 degrees. A similar increase to a lesser extent may be seen on a smooth glass surface as well as upon treating with FOTS. An increase in contact angle measurement is an indicator the surface was hydrophobic. Thus, AFM and contact angle measurements indicate the nanoporous glass surface is being modified sequentially after each step.

Optical wave guiding as a light-travelling means with fluorescence spectroscopy demonstrated the sensing behavior of functionalized nanoporous glass surface. Applicants found that the nanoporous layer does not scatter at least some light and so helps in increasing the waveguided light absorption of the Ru dye and collection of the emitted light. Also, the nanoporous layer enables better distribution of Ru dye due to a higher surface area. When a 450-nm absorbed light excited the Ru dye, the Ru dye emitted a light at 650 nm. The source for excited light is an light-emitting diode (LED) (FIG. 10(a)) and emission light is collected using a photodiode. Both components were attached to the back-surface side opposite to the sensing layer side, as shown in the Figure. Phase-angle-difference-based fluorescence sensing detection principle was used to quantify the waveguide-based sensing behavior. The procedure involves using excitation light in the form of a sine wave exciting the Ru dye and collecting emission light in the form of sine wave of the same frequency. The emission and excited sine waves are used to calculate the phase angle and intensity difference.

FIG. 10(b) shows the image of a multifunctional nanoporous glass coated with Ru dye and FOTS under excitation of a 450 nm LED and was taken when an oxygen-sensing test was conducted. Bright spots in the dye picture are the nanoporous glass layer coated with Ru dye. Upon exposure to a 100% nitrogen rich gas environment, bright spots got brighter, and the bright spots got less bright when the gas environment was changed to 90% nitrogen and 10% air. Oxygen gas present in the air interacts with Ru dye and decreases its emission. The difference in brightness with respect to switching the gas environment was easily seen when analyzing the emission signal from the photo diode. One such analysis is shown in FIG. 11. The oxygen sensing was measured in terms of a change in phase angle and intensity. The trend seen was in the presence of 10% air and 90% Nitrogen. The intensity decreased by 1-2 intensity units and phase increased by a 1 degree unit for the nanoporous glass surface. Sensing was repeated and reproducible as shown in FIG. 11, evidencing that functionalized nanoporous glass is a useful sensing platform.

To check for hydrophobicity and its influence on sensing, a known amount of water was added onto the nanoporous glass surface. The changes observed in the phase angle and intensity of the emission in the presence of water while doing a switching gas experiment is shown in FIG. 12. Changes in intensity are shown. The decrease in intensity in the presence of oxygen and vice versa, is identifiable in FIG. 12. The gas sensing pattern is identifiable before and during the addition of water, in the presence of water, and also after evaporation of water. This type of gas sensing in the presence of water is possible because of more than one functionality added to the surface. Thus, in addition to oxygen sensing, fluorescence intensity can be used to sense the formation and removal of water droplets using the same LED and photodiode.

Overall, a method to create a multifunctional glass surface enabled by the nanoporous surface layer for sensor application has been disclosed. Upon multi-functionalization, sensor behavior and hydrophobicity were retained on the glass surface and as a sensor that has a water repelling nature. In addition to sensing gas, addition and removal of the water droplets on the surface can be detected using the same optical elements.

According to an alternate embodiment, multifunctionalized surfaces can be created for various optical spectroscopic detection methods—Raman, Absorption, IR spectroscopy. In contemplated embodiments, a nanoporous surface as disclosed herein or a soot sheet (where the nanoporous structure extend through the sheet) may benefit from a hydrophobic coating, as disclosed herein, such as having a thickness (i.e. depth) of less than 100 nm. The glass soot may be silica, such as high purity fused silica. In contemplated embodiments, other than ion pairing, other chemical anchoring approaches of the sensing dye could be used on a nanoporous surface, such as ion-dipole or dipole-dipole interaction, hydrogen bonding and axial ligation. In contemplated embodiments, other processes for coating the dye could be used such dip coating, printing, etc. For hydrophobicity, other than FOTS, a long alkyl chain containing Silane could be used for example, or other materials. Mulitifunctionalized surfaces, as disclosed herein, could be used with other spectroscopic sensing detection methods such as absorption and Raman, surface plasmon. In contemplate embodiments, the multifunctionalization approaches disclosed herein could be used for nanoporous surfaces other than glass.

Referring to FIG. 13, an optical filter is on top of a photodiode as shown in FIG. 5, such as to further remove light from the excitation source (e.g., an LED). The waveguide optical sensing system as described above with regard to FIG. 5, may include a light filter located between the analyte area and the optical sensor such that light from the source is removed from the signal. A light filter may also be included between the analyte area and the optical sensor, or directly on top of the optical sensor.

Referring to FIG. 13, a waveguide optical sensing system, such as waveguide based glass sensor system 50, is shown according to an exemplary embodiment. Sensor system 50 is substantially the same as sensor system 10 except as discussed herein. Similar to sensor system 10, sensor system 50 includes an analyte area 18 that receives light 16, and light to be analyzed 22 leaves analyte area 18 to interact with photodiode 24. However, in the arrangement shown in FIG. 5, light source 14 and photodiode 24 are generally located on the same side of analyte area 18, and in particular are located adjacent to a common edge of glass sheet 12. In this arrangement, system 50 includes a light blocking structure 52 located between light source 14 and photodiode 24 such that light 16 is blocked from traveling directly from light source 14 to photodiode 24. This arrangement limits or prevents photodiode 24 from being saturated by direct light 16 allowing photodiode 24 to be responsive to or increase responsiveness to light to be analyzed 22.

Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that any particular order be inferred. In addition, as used herein, the article “a” is intended to include one or more component or element, and is not intended to be construed as meaning only one.

It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the disclosed embodiments. Since modifications, combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the embodiments may occur to persons skilled in the art, the disclosed embodiments should be construed to include everything within the scope of the appended claims and their equivalents. 

What is claimed is:
 1. A waveguide optical sensing system comprising: a light source configured to generate light having a wavelength; a waveguide formed from a light transmitting material, the waveguide having an input area, an output area, an outer surface and analyte area located along the outer surface, wherein the light from the light source enters the waveguide at the input area and travels within the waveguide by total internal reflection to the analyte area and light to be analyzed travels within the waveguide from the analyte area by total internal reflection to the output area; an optical sensor coupled to the output area, the optical sensor configured to interact with the light to be analyzed and configured to generate a signal related to a property of light to be analyzed; a plurality of pores located along the outer surface within the analyte area and formed in the light transmitting material of the waveguide; and a hydrophobic layer overlaying at least a portion of the pores.
 2. The waveguide optical sensing system of claim 1, wherein the pores have an average pore width, wherein the average pore width is less than 10% of the wavelength.
 3. The waveguide optical sensing system of claim 1, wherein the average pore width is less than 100 nm.
 4. The waveguide optical sensing system of claim 3, wherein the average pore width is greater than 1 nm and less than 30 nm.
 5. The waveguide optical sensing system of claim 1, further comprising a layer of a fluorescent analyte responsive material supported by the outer surface of the waveguide within the analyte area, wherein at least some of the fluorescent analyte responsive material is located within the pores, wherein the light to be analyzed comprises light generated by the fluorescent analyte responsive material, and the optical sensor is configured to generate a signal related to at least one of an intensity and a wavelength of the light to be analyzed, wherein the light transmitting material is glass.
 6. The waveguide optical sensing system of claim 5, wherein the light source is an LED, the optical sensor is a photodiode and the fluorescent analyte responsive material is an O₂ sensitive fluorophore.
 7. The waveguide optical sensing system of claim 1, further comprising a first light blocking structure located between the light source and the optical sensor such that light is blocked from traveling directly from the light source to the optical sensor.
 8. The waveguide optical sensing system of claim 7, further comprising: a second optical sensor configured to receive light from the light source and to generate a signal related to a property of the light generated by the light source; and a second light blocking structure located between the analyte area and the second optical sensor such that the light to be analyzed traveling away from the analyte area is blocked from directly traveling from the analyte area to the second optical sensor.
 9. The waveguide optical sensing system of claim 1, wherein the waveguide is at least a portion of a sheet of glass having a first major surface, a second major surface opposing the first major surface and a thickness between the first major surface and second major surface, wherein the outer surface of the waveguide is at least one of the first major surface and the second major surface.
 10. The waveguide optical sensing system of claim 9, wherein the analyte area and the plurality of pores are formed on the first major surface, and the input area and the output area are located along the second major surface.
 11. The waveguide optical sensing system of claim 10, wherein the sheet of glass has a thickness between 20 μm and 4 mm.
 12. A glass sensor system comprising: a sheet of glass material including a first major surface and a porous area located along the first major surface; a light source directing light into a first region of the sheet of glass material such that the light travels within the sheet of glass material by total internal reflection to the porous area where the light interacts with an analyte; and a light sensitive device coupled to a second region of the sheet of glass material, the light sensitive device interacting with light traveling from the porous area by total internal reflection to the second region, the light sensitive device configured to generate a signal related to a property of the light interacting with the light sensitive device; wherein the porous area includes a plurality of pores formed in the glass material and a hydrophobic layer overlaying the pores.
 13. The glass sensor system of claim 12, further comprising a layer of an analyte responsive material supported by the first major surface within the porous area, wherein at least some of the analyte responsive material is located within the pores, wherein the light from the light source interacts with the analyte by directly interacting with the analyte responsive material.
 14. The glass sensor system of claim 13, wherein the sheet of glass has a thickness between 20 μm and 4 mm, wherein the porous area occupies less than the entire area of the first major surface, wherein the analyte responsive material is a fluorescent analyte responsive material which is excited by the light from the light source, wherein the light that interacts with the light sensitive device comprises light generated by the fluorescent analyte responsive material during excitation by the light from the light source.
 15. The glass sensor system of claim 12, wherein the plurality of pores have an average depth of between 10 nm and 10 μm, wherein the average pore width is greater than 1 nm and less than 30 nm, wherein the light from the light source has a wavelength that is at least twenty times the average pore width.
 16. The glass sensor system of claim 15, wherein the first major surface is a substantially planar surface.
 17. A sensor waveguide configured for use as part of a sensing system, the sensor waveguide comprising: a sheet of light transmitting material comprising: a first major surface; a second major surface opposite the first major surface; an analyte contact area located on the first major surface; and a plurality of pores formed in the light transmitting material within the analyte contact area, wherein the pores have an average pore width of less than 100 nm; and a layer of an analyte responsive material supported by the first major surface within the analyte contact area, wherein at least some of the analyte responsive material is located within the plurality of pores a hydrophobic layer overlaying the layer of the analyte responsive material on an outer surface of the plurality of pores but not covering all of the analyte responsive material.
 18. The sensor waveguide of claim 17, wherein the plurality of pores have an average depth of between 10 nm and 10 μm, wherein the average pore width is greater than 1 nm and less than 30 nm, wherein the light transmitting material is a glass material, wherein sheet of glass material has an average thickness that is between 20 μm and 2 mm.
 19. The sensor waveguide of claim 17, wherein the analyte responsive material is a fluorescent analyte responsive material which fluoresces when excited by a light from a light source, wherein an amount of fluorescence of the fluorescent analyte responsive material is related to the presence of an analyte.
 20. The sensor waveguide of claim 19, wherein the fluorescent analyte responsive material is an O₂ sensitive fluorophore. 